WO2007135887A1 - Film orienté de polymère d'addition du composé norbornène seul, son procédé de production et son utilisation - Google Patents

Film orienté de polymère d'addition du composé norbornène seul, son procédé de production et son utilisation Download PDF

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Publication number
WO2007135887A1
WO2007135887A1 PCT/JP2007/059914 JP2007059914W WO2007135887A1 WO 2007135887 A1 WO2007135887 A1 WO 2007135887A1 JP 2007059914 W JP2007059914 W JP 2007059914W WO 2007135887 A1 WO2007135887 A1 WO 2007135887A1
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Prior art keywords
film
norbornene compound
polymer
norbornene
homoaddition
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PCT/JP2007/059914
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English (en)
Japanese (ja)
Inventor
Yoshihisa Takeyama
Atsushi Ishiguro
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Zeon Corporation
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Publication date
Application filed by Zeon Corporation filed Critical Zeon Corporation
Priority to CN2007800278208A priority Critical patent/CN101506279B/zh
Priority to JP2008516606A priority patent/JP5040915B2/ja
Priority to US12/301,760 priority patent/US8609005B2/en
Priority to EP07743349A priority patent/EP2028222B1/fr
Publication of WO2007135887A1 publication Critical patent/WO2007135887A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/009—After-treatment of articles without altering their shape; Apparatus therefor using gases without chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0038—Plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B29K2105/246—Uncured, e.g. green
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a stretched film of norbornene compound homoaddition polymer having a small linear expansion coefficient, which is suitably used for an electrical insulating component and an optical component. More specifically, the present invention relates to a norbornene compound homo-added polymer stretched film that hardly undergoes a dimensional change due to fluctuations in use environment temperature or humidity, or treatment with chemicals, a method for producing the same, and a use thereof. .
  • a film that is a polymer strength of norbornene compound has excellent heat resistance, transparency, chemical resistance and low water absorption, so that it can be used for optical parts, electrical insulation parts, electrical and electronic parts, and electronic parts. It is useful as a stopping material, medical equipment or packaging material.
  • the film used for these applications is required to have dimensional stability, particularly dimensional stability against temperature changes, that is, a low linear expansion coefficient. Specifically,
  • a linear expansion coefficient lower than 50 ppm is required.
  • the ring-opening polymer of a norbornene compound has a glass transition temperature of 200 ° C or lower and has a limited heat resistance.
  • it is normal to hydrogenate double bonds remaining after ring-opening polymerization, but even with a hydrogenation catalyst, a trace amount of double bonds still remain in the molecular chain.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-48060
  • Patent Document 2 JP-A-2005-126514
  • Patent Document 3 Japanese Patent Laid-Open No. 5-2108
  • Patent Document 4 JP-A-6-59121
  • Patent Document 5 Japanese Patent Laid-Open No. 2000-304920
  • Patent Document 6 Japanese Patent Laid-Open No. 2001-296422
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-133209
  • Patent Document 8 Japanese Patent Laid-Open No. 2006-18212
  • the norbornene compound polymer film having excellent film stability, no coloring problem, small linear expansion coefficient, and its simple use can be suitably used in the production process of electrical insulating parts and optical parts. New manufacturing methods are required.
  • the number average molecular weights of the polymers described in Patent Documents 3 to 8 are about 100,000.
  • the inventors of the present invention tried to form a film of a polymer with a norbornene compound having a number average molecular weight of this level by the solution casting method, the mechanical strength was insufficient and cracks were not generated. It was difficult to obtain a film.
  • the norbornene compound homoaddition polymer stretched film of the present invention preferably has a stretch ratio of 1.2 times or more and 10 times or less.
  • the norbornene compound homo-added polymer stretched film of the present invention is preferably a non-crosslinked film.
  • the norbornene compound homoaddition polymer stretched film of the present invention can be suitably obtained from a norbornene compound homoaddition polymer film having a number average molecular weight of 100,000 or more.
  • the norbornene compound homoaddition polymer stretched film of the present invention can be suitably obtained by norbornene compound homoaddition polymer film force produced by a solution casting method.
  • the norbornene compound single-added polymer stretched film having a linear expansion coefficient of 50 ppmZ ° C or less according to the present invention is obtained by converting the norbornene compound single-added polymer film into a norbornene compound single-added polymer film in an inert gas atmosphere.
  • the glass transition temperature (Tg) can be obtained by stretching in at least one direction within a temperature range of ⁇ 50 ° C.
  • the norbornene compound homoaddition polymer stretched film of the present invention is an organic compound having a boiling point of 1 to 200% by weight with respect to the norbornene compound homoaddition polymer of 250 ° C. or less. It is possible to obtain a norbornene compound homo-addition polymer film containing selenium by stretching it in at least one direction.
  • the norbornene compound homo-added polymer film is produced by a solution casting method, and the boiling point is 250 ° C. or less.
  • the organic compound is preferably the same compound as that used for film production by the solution casting method of norbornene compound homoaddition polymer film.
  • a stretched caropolymer film with a norbornene compound alone obtained by laminating a transparent conductive film.
  • an optical component an electrical insulating component, an electrical / electronic component, an electronic component sealing material, a medical device or a packaging material comprising the norbornene compound homoaddition polymer stretched film.
  • a norbornene compound polymer stretched film having excellent film stability, no coloration problem, and a low linear expansion coefficient can be obtained by a simple production method.
  • the norbornene compound homo-added polymer stretched film of the present invention is excellent in film stability and has a linear expansion coefficient of 50 ppmZ ° C or less, which eliminates the problem of coloring, so that it can be used for optical parts, electrical insulating parts, electrical and electronic parts. Useful in parts, electronic parts sealing materials, medical equipment and packaging materials.
  • the norbornene compound homoaddition polymer stretched film of the present invention (hereinafter sometimes simply referred to as "stretched film of the present invention") is a film formed by stretching a norbornene compound homoaddition polymer film. And has a linear expansion coefficient of 50 ppmZ ° C. or less.
  • Norbornene compound homoaddition polymer Norbornene compound homoaddition polymer used for the production of stretched films (hereinafter, simply referred to as “norbornene compound homoaddition polymer used in the present invention”) is a norbornene compound only. Is an addition polymer.
  • the norbornene compound homoaddition polymer used in the present invention is a kind of norbornene compound. It may be a polymer of a compound, or may be a copolymer of two or more types of norbornene compounds. However, in the case of a calopolymer with a copolymer of monomers other than norbornene compounds such as olefins. The object of the present invention cannot be achieved.
  • the norbornene compound homoaddition polymer used in the present invention is composed of a repeating structural unit represented by the general formula (1).
  • I ⁇ to R 4 are, independently of one another, a hydrogen atom; Periodic Table 15-16 heteroatom young properly Group to the functional group containing Kei atom; have or the functional group However, it is a hydrocarbon group having 1 to 20 carbon atoms. Further, I ⁇ to R 4 may be bonded to each other to form a ring. m is 0 or an integer of 1 or more.
  • Group heteroatoms of which are included in the functional group represented by 4 is not particularly limited constant, it can be exemplified an oxygen atom, a nitrogen atom and a sulfur atom .
  • functional groups include hydroxy, alkoxy, aryloxy, carbonyl, hydroxy carbo yl, alkoxy carbo yl, aryl carbo yl, functional groups containing oxygen atoms such as acid anhydride groups; Functional groups containing nitrogen atoms, such as arylamidocyan; functional groups containing oxygen and nitrogen atoms, such as aminoamino, alkylaminocarbol, and arylaminocarbonyl; mercapto, alkylthio, arylthio, etc.
  • a functional group containing a sulfur atom a functional group containing an oxygen atom and a sulfur atom such as thiocarbol; a functional group containing a key atom such as silyl, alkylsilyl, arylylsilyl, alkoxysilyl; And a functional group containing an oxygen atom and a key atom;
  • the hydrocarbon group represented by I ⁇ ⁇ R 4 is particularly preferably one having 1 to 20 carbon atoms. It is not limited. It may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a saturated group, or an unsaturated group. Furthermore, the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the hydrocarbon group may be one in which a part of carbon which may have the above functional group is substituted with a hetero atom or a key atom of Groups 15 to 16 of the periodic table.
  • the ring formed by the bonding I ⁇ to R 4 are each other, be saturated be unsaturated, also provides a condensed ring may be a single ring It doesn't matter.
  • the norbornene compound homoaddition polymer used in the present invention can be obtained by addition polymerization of a norbornene compound represented by the general formula (2).
  • Bicyclo [2.2.1] hept-2-enes used for the synthesis of norbornene compound homoaddition polymer used in the present invention is not particularly limited, but specific examples thereof include the following: Things can be mentioned.
  • Alkoxycarbon groups such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, 2-methyl-5-norbornene 2-methyl sulfonate, 2-methyl-5-norbornene 2-ethyl sulfonate Bicyclo [2.2.1] hept-2-enes having
  • Tetorashi black used in the synthesis of norbornene I ⁇ product alone addition polymer used in the present invention [6.2 1. I 3 '6 .0 2' 7.]
  • De de force - 4 E emissions such is particularly limited However, specific examples thereof include the following.
  • Tetracyclo [6.2.1. I 3 ' 6 .0 2 ' 7 ] Dode force 9 ene 4-methyl carboxylate and 4-methyltetracyclo [6.2. 1. I 3 ' 6 .0 2 '7] de de force one 9 E emissions such as methyl one 4-carboxylic acid alkoxycarbonyl -. tetracyclo with Le group [6.2 1. I 3' 6 .0 2 '7] de de force one 4- E down Kind;
  • Tetracyclo [6.2.1. I 3 '6 .0 2' 7] de de force one 9 E down one 4-methanol, and Tetorashiku port [6.2.1. I 3 '6 .0 2' 7] de de force one 9 Tetracyclo with 6 -ols and other hydroxy groups [6.2.1. I 3 '6.0. 2 ' 7 ] Dode force — 4-enes;
  • Tetracyclo [. 6.2.1 I 3 '6 .0 2' 7] de de force one 9 E down one 4-carboxyphenyl - tolyl, Tetorashiku port [. 6.2.1 I 3 '6 .0 2' 7] de de force one 9 E down one 4-carboxamide, and tetracyclo [6. 2. 1. I 3 '6 .0 2' 7] de de force - 9 E down - 4, 5 functional groups containing nitrogen atoms, such as dicarboxylic acid imide Tetracyclo [6.2.1. I 3 ' 6 .0 2 ' 7 ] Dode force-4 hens;
  • the norbornene compound homoaddition polymer used in the present invention is a bicyclo [2.2.1] hept-2-enes having no substituent or a hydrocarbon substituent from the viewpoint of dimensional stability and solubility.
  • Tetracyclo [6.2.1. I 3 '6.0 2 ' 7 ] dode force with substituted or hydrocarbon substituents-those in which the structural units derived from 4 enes occupy 70% or more of all repeating structural units are preferred Those with more than 80% are more preferred, those with more than 85% are more preferred, those with more than 95% are more preferred.
  • the hydrocarbon substituent is preferably one having 1 to 3 carbon atoms.
  • the norbornene compound homoaddition polymer used in the present invention comprises only the structural unit represented by the general formula (1).
  • the polymer has high heat resistance, and preferably has a glass transition temperature (Tg) of 200 ° C or higher, more preferably 220 ° C or higher, particularly preferably 240 ° C or higher.
  • Tg glass transition temperature
  • the glass transition temperature is lower than 200 ° C, heat resistance may be insufficient when used for some optical components and electrical insulation components.
  • the upper limit of the glass transition temperature is not particularly limited, but if it is higher than 400 ° C, the polymer may be decomposed, and it may be difficult to measure the glass transition temperature.
  • the norbornene compound homoaddition polymer used in the present invention preferably has a number average molecular weight (Mn) of 100,000 or more in terms of polystyrene.
  • the number average molecular weight is preferably 500,000 or less, more preferably force S, more preferably 120,000 to 450,000, and even more preferably 150,000-400,000. If the number average molecular weight is too high, the mechanical properties may be low, making it difficult to form a film. On the other hand, if the number average molecular weight is too large, the solution viscosity is too high and it may be difficult to produce a film.
  • the method for producing the norbornene compound homoaddition polymer used in the present invention is not particularly limited.
  • the polymerization catalyst is not particularly limited as long as it is a catalyst for addition polymerization of a norbornene compound.
  • nickel, palladium described in JP-T-11-505880, WO00Z20472, JP-A-2001-980359 A polymerization catalyst comprising a combination of a group 10 transition metal catalyst such as a promoter and a promoter such as an aluminum compound or a boron compound can be mentioned.
  • norbornene compound monoaddition polymers polymerized using a polymerization catalyst having a palladium atom are preferred because of their excellent mechanical properties.
  • the norbornene compound homoaddition polymer used in the present invention is such an olefinic unsaturated bond when the norbornene compound homoaddition polymer obtained by the above method has an olefinic unsaturated bond.
  • the bond may be hydrogenated.
  • the method for hydrogenation is not particularly limited.
  • the stretch ratio of the norbornene compound homo-added polymer stretched film of the present invention is preferably 1.2 times or more and 10 times or less. 1. It is 5 times or more and 6 times or less. Is more preferable It is particularly preferably 2 times or more and 4 times or less.
  • the draw ratio is less than 1.2 times, the effect of reducing the linear expansion coefficient may be reduced, and if it is more than 10 times, it is difficult to control the film thickness and the film may be easily cut during stretching. There is.
  • the stretched norbornene compound-added polymer stretched film of the present invention has a thickness of usually 1 to 1,000 O ⁇ m, preferably 2 to 500 / ⁇ ⁇ . Strictly speaking, “film” and “sheet” are distinguished by their thickness. In the present invention, “film” is a concept including both “film” and “sheet”. .
  • the norbornene compound homoaddition polymer stretched film of the present invention is preferably a non-crosslinked film.
  • the film By being non-crosslinked, the film can be easily stretched at a high magnification without causing breakage of the film during stretching.
  • Whether the film is cross-linked or non-cross-linked is determined by the solubility of the film in the solvent. Specifically, the film lg is immersed in 1 OOg of the solvent used in the solution casting method described later, shaken at room temperature for one day and night, and then the film that does not maintain the film shape is uncrosslinked.
  • the norbornene compound homoaddition polymer stretched film of the present invention has a linear expansion coefficient of 50 ppmZ ° C or less.
  • the linear expansion coefficient is preferably 45 ppm or less, more preferably 40 ppm or less.
  • the norbornene compound homoaddition polymer stretched film having a linear expansion coefficient of 50 ppm, ° C or less of the present invention can be obtained by stretching the norbornene compound homoaddition polymer film. .
  • the thickness of the norbornene compound homoaddition polymer film used in the present invention is not particularly limited, and is usually 1 to 1,000 ⁇ m, preferably 2 to 500 ⁇ m. If the thickness is less than 1 ⁇ m, the strength of the film is weak, and it is difficult to prepare a stretched film of 1,000 m or more at a high stretch ratio as soon as defects occur.
  • the norbornene compound homo-addition polymer film used in the present invention can be suitably produced by a solution casting method.
  • Norbornene composite polymer film production method In addition to the solution casting method, there is a melt extrusion method. In this method, since the glass transition temperature of the norbornene compound polymer is high, it is necessary to adopt molding conditions that are considerably high, For this reason, the obtained film is unsuitable for optical applications where coloring is intense.
  • a solution in which a norbornene compound homoaddition polymer is dissolved or dispersed in an organic solvent is used by using a die coater to form a metal drum, steel belt, polyethylene terephthalate (PET) or polyethylene naphthalate.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • PEN phthalate
  • a support such as a polytetrafluoroethylene belt
  • the solution may be applied to the support by spraying, brushing, roll spin coating, dating, etc., and then the solvent is dried to peel off the support strength film.
  • thickness, surface smoothness, etc. are controllable by apply
  • the solvent used in the solution casting method is not particularly limited as long as it dissolves or disperses the norbornene compound homo-addition polymer.
  • aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclohexane.
  • Alicyclic hydrocarbons such as decane, hexahydroindene, cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene; halogen-containing aliphatic hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane; Halogen-containing aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene; Nitrogen-containing solvents such as nitromethane, nitrobenzene, and acetonitrile; Aliphatic ethers such as jetyl ether and tetrahydrofuran; Aromatic ethers such as ether and phenetole And the like.
  • aromatic hydrocarbons aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and halogen-containing solvents are preferable.
  • solvents that does not dissolve the caropolymer with norbornene compound alone for the purpose of lowering the solution viscosity.
  • solvents include cellosolve solvents such as methyl solvate solve, ethinorecero soleb, 1-methoxy 1-2-propanol; diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4 Examples include ketone solvents such as methyl-2-pentanone; ester solvents such as methyl lactate and ethyl lactate; and alcohol solvents such as 1 pentanol and 1-butanol.
  • the concentration of the polymer in dissolving or dispersing the norbornene compound homoaddition polymer in a solvent is preferably 0.1 to 50% by weight, more preferably 0.2 to 45% by weight. ⁇ 40 wt% is especially preferred U ,. If the concentration of the polymer is less than the above lower limit, it becomes difficult to ensure the thickness of the film, and there may be a problem that the surface smoothness of the film is obtained due to foaming due to solvent evaporation. . On the other hand, if the concentration exceeds the above upper limit, the solution viscosity becomes too high, and the thickness and surface of the resulting film become uniform.
  • the viscosity of the solution at room temperature is usually 1 to 1,000,000 mPa-s, preferably 10 to 100,000 mPa-s, more preferably 100 to 50,000 mPa-s, and particularly preferably 1,000. ⁇ 40,000mPa, s.
  • the film is usually formed at room temperature.
  • the polymer is formed.
  • the solution may be preheated.
  • the temperature to be heated is a force depending on the boiling point of the solvent used 30 ° C to 250 ° C, preferably 40. C ⁇ 200. C.
  • the drying step in the solution casting method is not particularly limited and can be carried out by a commonly used method, for example, a method of passing through a drying furnace through a large number of rollers. If air bubbles are generated, the film characteristics will be drastically deteriorated. To avoid this, the drying process is divided into two or more stages, and the temperature or air volume is controlled appropriately for each process. Is preferred.
  • the norbornene compound homoaddition polymer film is stretched in an inert gas atmosphere within the temperature range of the glass transition temperature (Tg) ⁇ 50 ° C of the norbornene compound homoaddition polymer film. I prefer to do that.
  • the stretching temperature should be within the glass transition temperature (Tg) ⁇ 40 ° C temperature range of the glass transition temperature (Tg) ⁇ 45 ° C of the norbornene compound homoaddition polymer film. Is more preferable.
  • Glass transition temperature (Tg) of norbornene compound homo-added polymer film Desired coefficient of linear expansion without breaking the film by stretching within a temperature range of 50 ° C A stretched film having can be obtained.
  • the stretching ratio does not increase and the resulting stretched film is colored. However, it is inferior in mechanical strength and becomes brittle.
  • the residual solvent in the norbornene compound single addition polymer film (specific examples are the solvent used for the preparation of the norbornene compound single addition polymer film by the solution casting method).
  • the amount of is preferably 5,000 ppm by weight or less, more preferably 1,000 ppm by weight or less, based on the norbornene compound homoaddition polymer.
  • the stretched film of the present invention is provided with a norbornene compound alone containing an organic compound having a boiling point of 250 ° C or less at normal pressure of 1 to 200% by weight based on the norbornene compound homoaddition polymer.
  • the polymer film can also be obtained by stretching in at least one direction.
  • the lower limit of the stretching temperature is not particularly limited, but is usually room temperature, and the upper limit is not particularly limited, but from the viewpoint of operation, the glass transition temperature (Tg) of the norbornene compound homo-addition polymer film Is preferred.
  • the inclusion of the organic compound reduces the apparent glass transition temperature of the norbornene compound single addition polymer film, so the norbornene compound single addition polymer itself. It is possible to stretch at a temperature lower than the glass transition temperature. If the organic compound is removed by drying after stretching, a norbornene compound homoaddition polymer stretched film can be obtained.
  • the organic compound having a boiling point of 250 ° C or less to be contained in the norbornene compound homo-addition polymer film uniformly penetrates into the norbornene compound homopolymer and has a boiling point of 250 ° C or less. If it is the organic compound of, it will not specifically limit.
  • the boiling point of these organic compounds is preferably 40 to 230 ° C, more preferably 50 to 200 ° C.
  • Specific examples of the solvent to be included in the norbornene compound homoaddition polymer film should be the same as those used for the preparation of the norbornene compound homoaddition polymer film by the solution casting method. Can do.
  • the boiling point is 250.
  • Organic compound strength at or below ° C It is preferable that the same compound as used in the preparation of a norbornene compound homoaddition polymer film by the solution casting method. Thereby, a norbornene compound homoaddition polymer film and a norbornene compound homoaddition polymer stretched film can be easily obtained.
  • the amount of the organic compound in the norbornene compound homo-addition polymer film is preferably 1 to 200% by weight based on the norbornene compound homo-addition polymer, and 2 to 150% by weight. It is more preferable to be 3%: LOO% by weight is particularly preferable.
  • the method of setting the amount of the organic compound to be contained in the norbornene compound homoaddition polymer film within the above range is not particularly limited. Specific methods include, for example, a method in which the solvent is left in the film so as to be in the above range when the film is produced by the solution casting method, and a method in which the organic compound is permeated into the norbornene compound homoaddition polymer film. It is done.
  • Stretching is performed in at least one direction.
  • a film having birefringence can be obtained by uniaxial stretching.
  • a film having a small birefringence can be obtained by biaxial stretching.
  • the stretching speed is not particularly limited, but is preferably 10 to 5,000% Z, and more preferably 20 to 2,000% Z.
  • the stretching method may be any device as long as it can be uniformly stretched uniaxially or biaxially.
  • the film piece is stretched in a uniaxial or biaxial direction with a stretching device such as Tensilon. Stretch to.
  • a stretching device such as Tensilon. Stretch to.
  • the tenter method can be used in the case of stretching in the transverse direction using the method of using a roll with different peripheral speeds.
  • the stretching is desirably performed in an inert gas atmosphere. This makes it possible to obtain a stretched film having a desired coefficient of linear expansion that does not cause breakage, coloring, or deterioration of the film.
  • the inert gas is not particularly limited, and nitrogen, carbon dioxide gas, rare gas, or the like can be used.
  • the residual solvent in the stretched film (such as the organic compound having a boiling point of 250 ° C. or lower) may be reduced to a desired range by a conventionally known drying method such as heating and vacuum drying after stretching.
  • the norbornene compound homoaddition polymer stretched film of the present invention preferably contains an antioxidant.
  • an antioxidant stability at high temperatures can be improved.
  • the anti-oxidation agent is not particularly limited, but it is preferably at least one selected from the group power that also includes phenolic anti-oxidation agents, rataton-based antioxidants, and phosphorus-based anti-oxidation agents. It is more preferable to use two or more of these in combination in order to enhance the effect of preventing acid and soot.
  • phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 4,4, -thiobis (6-tri-butyl-3-methylphenol), 1,1, -bis (4 — Hydroxyphenyl) cyclohexane, 2,2,1-methylenebis (4 ethyl 6-tert-butylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3— (3,5-Di-tert-butyl 4-hydroxyphenol) propionate, 3, 3 ′, 3 ", 5, 5 ', 5" —hexer tert-butyl a, a', a,, — ( Mesitylene—2, 4, 6 triyl) tri—p cresol, 1, 3, 5 tris (3,5 di-tert-butyl 4-hydroxybenzyl) 1, 3, 5 triazine 1,
  • phosphorus antioxidants include tris (4-methoxy-1,3,5 diphenyl) phosphite, tris (noulefel) phosphite, tris (2,4 di-t-butylphenol). Phosphite, tris [2— [[2, 4, 8, 10—tetra-tert-butyldibenzo [d, f] [l, 3, 2] dio And xaphosphephine-1-yl] oxy] ethyl] amine.
  • Specific examples of the rataton-based antioxidation agent include a reaction product of 3-hydroxy-5,7-di-butyl-furan-2-one and o-xylene.
  • the addition amount of these anti-oxidation agents is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the norbornene compound homoaddition polymer. .
  • heat-resistant cage stabilizers examples include hydroxylamine-based heat-resistant cage stabilizers; Zio-type heat-resistant such as didodecyl 3, 3, monothiodipropionate, dioctadecyl 3, 3, monothiodipropionate, etc. Processing stabilizers; and the like.
  • UV absorbers examples include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers.
  • light stabilizers examples include benzoate light stabilizers, hindered amine light stabilizers, and the like.
  • the norbornene compound homoaddition polymer stretched film may contain various additives as required.
  • additives examples include inorganic fillers, organic fillers, processing stabilizers, antistatic agents, near infrared absorbers, colorants such as dyes and pigments, phosphors, lubricants, plasticizers, flame retardants, and crosslinking agents. Etc.
  • the method of adding an antioxidant and other additives to the norbornene compound homoaddition polymer stretched film is that the antioxidant and other additives can be uniformly dissolved or dispersed in the film of the present invention. Any method can be used as long as it is a solution, but there is a method in which a solution casting film is prepared after dissolving or dispersing in a solution for casting a norbornene compound homoaddition polymer used for producing a stretched film. Simple and preferred.
  • the norbornene compound homo-added polymer stretched film of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more. It can be suitably used as an element member.
  • [0057] [Transparent conductive film laminate film]
  • the norbornene compound homo-added polymer stretched film of the present invention may be a laminate of transparent conductive films (hereinafter sometimes referred to as “transparent conductive film laminate film”).
  • the transparent conductive film layer As a material for forming the transparent conductive film layer (transparent conductive film), metals such as Sn, In, Ti, Pb, Au, Pt, Ag, or oxides thereof such as indium oxide Tin (ITO), aluminum oxide, silicon oxide, titanium oxide, zinc oxide, tungsten oxide, aluminum nitride, silicon nitride, titanium nitride, sodium cadmium sulfate, zinc sulfide, zinc selenide, etc. Generally used. These single metal films can be formed on a substrate, and if necessary, this single metal film can be oxidized to form a transparent conductive film layer.
  • ITO indium oxide Tin
  • a metal oxide layer is deposited from the beginning of the film formation, but at the beginning of the film formation, the film is formed in the form of a simple metal or a lower oxide, and then heat oxidation, anodization, or liquid phase oxidation. It can also be made transparent by subjecting it to oxidation treatment.
  • These transparent conductive film layers may be formed by adhering a sheet, film or the like having another transparent conductive film layer to a norbornene compound homoaddition polymer stretched film, plasma polymerization method, sputtering It may be formed directly on the norbornene compound homo-added polymer stretched film by a method, a vacuum deposition method, a plating method, an ion plating method, a spray method, an electroanalysis method or the like.
  • the thickness of these transparent conductive film layers is appropriately determined depending on desired properties and is not particularly limited, but is usually 10 to: LO, OOOA, preferably 50 to 5, OOOA.
  • an adhesive layer and an anchor coat layer may be formed.
  • the adhesive layer can be formed using a heat-resistant resin such as epoxy resin, polyimide, polybutadiene, phenol resin, or polyether ether ketone.
  • the anchor coat layer is cured by a known curing method such as UV curing or heat curing using an anchor coating agent including acrylic prepolymers such as epoxy ditalylate, urethane ditalylate, and polyester ditalylate. Can be formed.
  • a norbornene compound homoaddition polymer An adhesive layer may be provided between the film and the transparent conductive film for the purpose of improving the smoothness of the film and the adhesion with the transparent conductive film.
  • the adhesive layer can be obtained by applying a varnish varnish and removing the solvent by drying. At this time, a resin having film-forming properties after removal of the solvent, that is, a varnish to which a solid resin is added is preferable from the viewpoint of uniform application.
  • the resin used for this purpose include photo-curable resins such as epoxy prepolymers such as epoxy diatalylate, urethane diatalylate, and polyester diatalylate; o Cresolol novolac type, bisphenol type Epoxy-based, urethane-based, acrylic-based, urea-based, melamine-based and unsaturated polyester-based thermosetting resins; electron beam-curable resins.
  • photocurable resin is preferable in terms of productivity and cost.
  • any method for forming the cured resin coating any method having a gravure coating method, a reverse roll coating method, a kiss roll coating method, or the like may be used.
  • the transparent conductive film laminated film of the present invention may have a gas noble layer on the side opposite to the transparent conductive film.
  • the gas noble layer may be formed of an inorganic material or an organic material.
  • the inorganic material that can be used include silicon oxide, aluminum oxide, indium oxide, and the like, and examples of the organic material include polybutyl alcohol, ethylene butyl alcohol copolymer, and polyamide.
  • the film thickness of the gas layer is 100-2, OOOA for inorganic materials and 500 for organic materials.
  • inorganic materials can be formed by known means such as sputtering, ion plating, resistance heating, and CDV.
  • a film can be formed by dissolving it in a solvent, applying it by the coating method as described above, and drying it.
  • an adhesive layer may be provided between the film and the gas noble layer.
  • a protective coat layer may be laminated on the gas barrier layer to protect it.
  • the protective coating layer is preferably formed by the same method as the adhesive layer.
  • the norbornene compound homo-added polymer stretched film of the present invention includes a color filter substrate, a light guide plate, a protective film, a polarizing film, a retardation film, a touch panel, Suitable for use as optical parts such as transparent electrode substrates, optical recording substrates such as CD, MD, DVD, TFT substrates, liquid crystal display substrates, organic EL display substrates, optical transmission waveguides, optical element sealing materials, etc. can do.
  • members for display elements specifically color filter substrates, light guide plates, protective films, polarizing films, retardation films, touch panels, transparent electrode substrates, TFT substrates, liquid crystal display substrates, organic EL display substrates, etc.can be suitably used.
  • a color filter can be obtained by laminating one color filter layer on the stretched film of the norbornene compound homoaddition polymer of the present invention or the transparent conductive film laminate film of the present invention.
  • a lamination method a known pigment dispersion method, dyeing method, electrodeposition method, printing method, transfer method, or the like can be used.
  • the above color filter can be used as a color filter for a liquid crystal display device, and can also be used as a part of components such as a color display and a liquid crystal display device.
  • the norbornene compound homo-added polymer stretched film of the present invention is used not only for optical parts but also for electrical insulating parts, electrical and electronic parts, electronic parts sealants, medical equipment, and packaging materials. be able to.
  • the norbornene compound homoaddition polymer stretched film of the present invention is excellent in heat resistance and electrical properties, and is small as a dimensional change even when subjected to high temperature treatment or chemical treatment, and is therefore optimal as an electrical insulation component.
  • Examples of electrical insulation parts include power cables and cable coating materials, insulation materials for office automation equipment such as computers, printers, and copiers, and insulation parts for flexible printed circuit boards. Particularly suitable for use as flexible printed circuit boards. It is done.
  • Example 1 As medical equipment, it is used for chemical containers, infusion bags, sample containers, sterilization containers, tubes, etc.
  • test and evaluation in an Example and a comparative example were performed with the following method.
  • the dynamic viscoelasticity is measured using a viscoelastic spectrometer (trade name “EXST AR DMS6100” manufactured by Seiko Instruments Inc.) with a measurement frequency of 10 Hz, a heating rate of 5 ° CZ, and an excitation mode. Measure the temperature at the inflection point of the storage elastic modulus E 'using a single waveform with an excitation amplitude of 5.0 m.
  • the norbornene compound homo-addition polymer film is dissolved in a solvent other than the solvent used to prepare the norbornene compound homo-addition polymer film, and then quantitatively determined using gas chromatography.
  • JASCO UV-visible spectrometer
  • TMA Thermal Mechanical Analyzer
  • SDTA840 Thermal Mechanical Analyzer
  • METRA ⁇ Toledo Co., Ltd. a test piece shape of 15.4 mm in length and 5.95 mm in width is fixed upright and fixed. And apply a lg weight load with the probe. Temperature is increased from room temperature to 5 ° CZ, and the temperature (horizontal axis) —elongation of the film piece (vertical axis) is plotted on a graph, and the elongation force of the film piece between 30 ° C and 200 ° C is linearly expanded. Find the rate.
  • TMA Thermal Mechanical Analyzer
  • a nitrogen-substituted glass reactor was charged with 0.77 parts of (aryl) palladium (tricyclohexylphosphine) chloride and 14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene. was added to prepare a catalyst solution.
  • the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C for 18 hours, and polymer (a) 2, 462 parts were obtained.
  • the number average molecular weight (hereinafter sometimes abbreviated as “Mn”) of the polymer (a) is 222,000, and the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) is 725,000.
  • the NB unit ZEtNB unit composition ratio in the polymer (a) is 70Z30 (mol Z mol), and the glass transition temperature (Tg) is 281. . Met.
  • a 10% toluene solution of polymer (a) was prepared, and octadecyl 3- (3 , 5 Di-tert-butyl-4-hydroxyphenol) propionate to 0.5% of polymer (a) and Tris (2,4-dibutylphenol) phosphite to polymer (a) 1.
  • the reaction product of 0%, 3hydroxy-1,5,7di-tert-butyl-furan-2-one and o-xylene was dissolved by adding 0.3% to the polymer (a).
  • the linear expansion coefficient of this norbornene compound homoaddition polymer film (1) was 64 ppmZ ° C.
  • a nitrogen-substituted glass reactor was charged with 0.77 parts of (aryl) palladium (tricyclohexylphosphine) chloride and 14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene. was added to prepare a catalyst solution.
  • the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C for 18 hours, and polymer (b 2, 4 23 parts were obtained.
  • the number average molecular weight (hereinafter sometimes abbreviated as “Mn”) of the polymer (b) is 157,000, and the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) is 487,000.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the NB unit ZEdNB unit composition ratio is 70Z30 (mol Z mol), and the glass transition temperature (Tg) is 284. C.
  • a 10% toluene solution of the polymer (b) was prepared, and octadecyl 3- (3,5 di-tert-butyl-4-hydroxyphenol) propionate was used as an antioxidation agent for the polymer (b).
  • the reaction product of 3-hydroxy-1,5,7-di-tert-butyl-furan-2-one and o-xylene was dissolved by adding 0.3% to the polymer (b).
  • the linear expansion coefficient of this norbornene compound homo-addition polymer film (2) was 60 ppm Z ° C.
  • the norbornene compound homoaddition polymer film (1) obtained in Reference Example 1 was set in an electric type-shaft extension machine (trade name “IMC-16BE” manufactured by Imoto Seisakusho Co., Ltd.). After replacing the inside of the sample chamber with nitrogen, it was heated to 310 ° C, and the film was stretched twice at a stretching rate of 55% Z.
  • IMC-16BE electric type-shaft extension machine
  • the obtained stretched film was completely dissolved in toluene and did not leave a film shape. Therefore, the stretched film was non-crosslinked and the linear expansion coefficient was 41 ppm. The light transmittance was 91%.
  • the norbornene compound homo-addition polymer film (2) obtained in Reference Example 2 was impregnated with diethylene glycol ether methyl ether (boiling point 179 ° C) for 30 minutes, and the polymer film (2) was diethylene glycol ester. 50% til methyl ether was contained.
  • the resulting solvent-containing film was stretched twice using an electric uniaxial stretching machine (trade name “IMC-16BE”, manufactured by Imoto Seisakusho Co., Ltd.) at 100 ° C. in an air atmosphere at a stretching speed of 55% Z min. .
  • diethylene glycol ethyl methyl ether was removed by evaporation at 180 ° C for 3 hours in a nitrogen atmosphere, and then further vacuum-dried at 180 ° C for 18 hours.
  • the residual solvent amount was less than 5 OOppm.
  • a stretched Finolem with a film thickness of 45 ⁇ m was obtained.
  • the obtained stretched film was completely dissolved in toluene and did not leave a film shape. Therefore, the stretched film was non-crosslinked and the linear expansion coefficient was 35 ppm. The light transmittance was 91%.
  • the norbornene compound homoaddition polymer film (1) obtained in Reference Example 1 was set in an electric type-shaft extension machine (trade name “IMC-16BE” manufactured by Imoto Seisakusho Co., Ltd.). Air atmosphere sump When the film was stretched at a stretch rate of 55% Z in a Lucy bar at a temperature of 310 ° C, it was cut at a stretch ratio of less than 1.2.
  • the obtained stretched film was yellowed and mechanical strength was very low and fragile, so that the linear expansion coefficient could not be measured.
  • the norbornene compound homoaddition polymer film (1) obtained in Reference Example 1 was set in an electric type-shaft extension machine (trade name “IMC-16BE” manufactured by Imoto Seisakusho Co., Ltd.). When trying to stretch at 100 ° C in a sample chamber in an air atmosphere, it was hardly stretched and cut at a draw ratio of less than 1.1 times. The linear expansion coefficient of this film was 63 ppm, and it was impossible to reduce the linear expansion coefficient to 50 ppm or less.
  • a norbornene compound single addition polymer film was subjected to a glass transition temperature (Tg) of ⁇ 50 ° C in an inert gas atmosphere.
  • Tg glass transition temperature
  • the norbornene compound homo-addition polymer film when stretched in an air atmosphere, the stretch ratio cannot be increased, and the resulting low stretch ratio film turns yellow and has a very high mechanical strength. It can be seen that it is low and brittle. Further, since the norbornene compound homoaddition polymer film does not contain an organic compound, it cannot be stretched by 1.2 times or more even if it is stretched at a lower temperature (Tg-50).

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Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à proposer un film orienté de polymère d'addition du composé norbornène seul qui est approprié pour une utilisation dans des procédés de fabrication de pièces d'isolation électrique ou de pièces optiques, et qui excelle en termes de stabilité de film, lequel étant dépourvu de problèmes de taches et exhibant un faible coefficient d'expansion linéaire et à proposer un procédé facile pour sa production. La solution proposée consiste à proposer un film orienté de polymère d'addition du composé norbornène seul, lequel étant un film obtenu en étirant un film du polymère d'addition du composé norbornène seul et exhibant un coefficient d'expansion linéaire inférieur ou égal à 50 ppm/°C. De préférence, le rapport d'étirage est dans la gamme de 1,2 à 10. Le film orienté est de préférence un film non-réticulé. En outre, on propose un procédé de production d'un film orienté, comprenant au moins un étirage unidirectionnel d'un film du polymère d'addition du composé norbornène seul sous une atmosphère de gaz inerte à une température dans la gamme de la température de transition vitreuse de celui-ci ± 50 °C, ou au moins un étirage unidirectionnel d'un film du polymère d'addition du composé norbornène seul imprégné d'un composé organique de température d'ébullition spécifique.
PCT/JP2007/059914 2006-05-23 2007-05-15 Film orienté de polymère d'addition du composé norbornène seul, son procédé de production et son utilisation WO2007135887A1 (fr)

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US12/301,760 US8609005B2 (en) 2006-05-23 2007-05-15 Stretched film of addition polymer consisting of norbornene compound, process for producing the same and use thereof
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CN101506279B (zh) 2012-06-06
US8609005B2 (en) 2013-12-17
JPWO2007135887A1 (ja) 2009-10-01
US20090182117A1 (en) 2009-07-16
TW200804479A (en) 2008-01-16
KR20090028527A (ko) 2009-03-18
EP2028222A4 (fr) 2011-09-07
CN101506279A (zh) 2009-08-12
EP2028222A1 (fr) 2009-02-25
JP5040915B2 (ja) 2012-10-03

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